Self repairing process for porous dielectric materials

ABSTRACT

The present disclosure relates to a structure and method to create a self-repairing dielectric material for semiconductor device applications. A porous dielectric material is deposited on a substrate, and exposed with treating agent particles such that the treating agent particles diffuse into the dielectric material. A dense non-porous cap is formed above the dielectric material which encapsulates the treating agent particles within the dielectric material. The dielectric material is then subjected to a process which creates damage to the dielectric material. A chemical reaction is initiated between the treating agent particles and the damage, repairing the damage. A gradient concentration resulting from the consumption of treating agent particles by the chemical reaction promotes continuous diffusion the treating agent particles towards the damaged region of the dielectric material, continuously repairing the damage.

BACKGROUND

The scaling of semiconductor feature sizes according to Moore's Law hasdriven a need for improved material properties to achieve a desiredintegrated circuit performance. Some aspects of integrated circuitperformance may be enhanced through the utilization of a dielectricmaterial with a low dielectric constant for electrical isolation ofmetallization levels. The processing steps required to manufacture thevarious components of an integrated circuit can degrade the propertiesof the dielectric material, reducing yield. As such, efficient repairmechanisms are desired.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1A-FIG. 2B illustrate some embodiments of a self-repairingdielectric material.

FIG. 3A illustrates a table describing four dielectric samples for XPSmeasurements of carbon concentration.

FIG. 3B illustrates a carbon depletion profile for some embodiments ofself-repairing dielectrics vs. externally-repaired dielectrics.

FIG. 4 illustrates a flow diagram of some embodiments of a method tocreate a self-repairing dielectric structure.

DETAILED DESCRIPTION

The description herein is made with reference to the drawings, whereinlike reference numerals are generally utilized to refer to like elementsthroughout, and wherein the various structures are not necessarily drawnto scale. In the following description, for purposes of explanation,numerous specific details are set forth in order to facilitateunderstanding. It may be evident, however, to one of ordinary skill inthe art, that one or more aspects described herein may be practiced witha lesser degree of these specific details. In other instances, knownstructures and devices are shown in block diagram form to facilitateunderstanding.

Semiconductor manufacturing involves a series of photolithography steps,wherein a semiconductor workpiece, comprising a dielectric material on asilicon substrate, is coated with photoresist, aligned with a patterningmask, and exposed to a radiation source. The radiation creates a patternof developed photoresist corresponding to the open regions of thephotomask. The semiconductor workpiece is then subjected to an etchprocess, which creates openings in the dielectric material. The etchprocess may also introduce damage to the dielectric material, the damagecomprising a reduction in a concentration of carbon containing moietiesnear a surface region of the dielectric material. Electron energy lossspectroscopy (EELS) measurements of damaged dielectric material indicatethat the damaged surface region extends to depths of approximately 40angstroms. This damaged surface region results in a higher interconnectcapacitance between metallization layers formed within the dielectricmaterial, which degrades the electrical performance of the metallizationlayers by introducing additional RC delay. To mitigate some of theseeffects, the damage may be reacted with treating agent particles toincrease the concentration of carbon containing moieties in the damagedsurface region of the dielectric material, thus repairing the dielectricmaterial. The treating agent particles react with the damaged surfaceregion by functional chemical group, and do not easily penetrate intothe damaged surface region. X-ray Photoelectron Spectroscopy (XPS)measurements indicate the penetration depth of treating agent particlesto be less than 20 angstroms. Therefore, the treating agent particles donot diffuse far enough into the dielectric material to completely repairall of the damage. As a result, the RC delay is not completelyeliminated.

The scaling of semiconductor feature sizes according to Moore's Law hasdriven a need for improved material properties to achieve a desiredintegrated circuit performance. Some aspects of integrated circuitperformance may be enhanced through the utilization of a dielectricmaterial for electrical isolation of metallization levels, wherein adielectric constant (k) of the dielectric material defines an ability ofthe dielectric material to withstand maintain electrical potentialbetween electrically-isolated metallization levels. The processing stepsrequired to manufacture the various components of an integrated circuitcan degrade the properties of the dielectric material, reducing yield.As such, efficient repair mechanisms are desired.

Accordingly, the present disclosure relates to a structure and method torepair damage created in a dielectric material during a manufacturingprocess. A dielectric material is formed on a substrate, and exposedwith treating agent particles such that the treating agent particlesdiffuse into the dielectric material and form a substantially uniformconcentration within the dielectric material. A cap is then formed abovethe dielectric material to encapsulate the treating agent particleswithin the dielectric material. The dielectric material is thensubjected to a process (e.g., etching, ashing, chemical cleaning, orthermal cycling) which induces damage to the dielectric material. Thetreating agent particles encapsulated within the dielectric materialthen diffuse through the dielectric material and react with the damageto repair the dielectric material.

FIG. 1A illustrates some embodiments of a self-repairing dielectricmaterial 100A. A copper metallization layer 102 formed. Above the coppermetallization layer 102 a dielectric film 104 is formed, and separatedfrom the copper metallization layer 102 by an etch stop liner 106, whichprevents subsequent etch and clean steps within the dielectric film 104from interacting with the copper metallization layer 102. After a curingstep comprising exposure to ultraviolet radiation for a time period ofapproximately 3 minutes to approximately 6 minutes, the dielectric film104 is then exposed with treating agent particles 108, which comprisesone or more of liquids, vapors, gases, plasmas, supercritical solvents,or combinations thereof. The treating agent particles comprise atreating agent particle size of approximately C₁-C₁₈. In someembodiments, the formation of the dielectric film 104 and an exposure totreating agent particles 108 is carried out in-situ (i.e., in a singleprocessing chamber) in a single processing step. In other embodiments,the formation of the dielectric film 104 and an exposure to treatingagent particles 108 comprises multiple processing steps carried out in aplurality of processing chambers.

The dielectric film 104 is porous with a pore size ranging fromapproximately 11 angstroms to approximately 20 angstroms, which islarger than the treating agent particle size of the treating agentparticles 108, such that the treating agent particles diffuse into thedielectric material and form a substantially uniform concentrationwithin the dielectric material. The substantially uniform concentrationcomprises less than approximately 5% variation in a concentration oftreating agent particles 108. FIG. 1B illustrates some embodiments of aself-repairing dielectric material 100B, wherein a non-porous capmaterial 110 is formed above the dielectric film 104. The non-porous capmaterial 110 comprises a pore size of essentially zero, such that thenon-porous cap material 110 encapsulates the treating agent particles108 within the dielectric film 104. In some embodiments the non-porouscap material 110 comprises a porous ultra low-k dielectric material suchas oxygen-doped SiC (ODC), nitrogen-doped SiC (NDC), SiN, etc.,comprising a dielectric constant value of less than approximately 2.4.

FIG. 2A illustrates some embodiments of a self-repairing dielectricmaterial 200A. Openings 202 are formed in the dielectric film 104 by anetch and clean process (e.g., a plasma etch followed by a chemicalclean), which introduces sidewall damage 204 within a surface region ofthe dielectric film 104. A chemical reaction is initiated between thetreating agent particles 108 and the sidewall damage 204, essentiallycompletely repairing the damage within the surface region for any depth.The chemical reaction my occur automatically as the sidewall damage 204forms, or may be initiated by an activation process comprising ahigh-temperature process, ultra-violet cure, or otherenergy-transferring process.

For the embodiments of the self-repairing dielectric material 200A, thedielectric film 104 comprises a carbon containing SiO₂ film such as anSiCOH-based porous low-k dielectric material, comprising a dielectricconstant value between approximately 2.4 and approximately 3.0, whereincarbon has been added to reduce the polarizability thus reducing adielectric constant of the dielectric film 104. Subsequent processingsteps such as plasma etching or ashing are found to cause depletion ofcarbon containing moieties within the surface region of the dielectricfilm 104, replacing Si—CH₃ bonds with Si—OH bonds. In porous low-kdielectric materials reactive etch and ash gases may diffuse furtherinto the film, thus increasing the range of damage. For instance, whenthe dielectric film 104 is plasma etched with plasma containing Ar andfree radicals such as O, F, N, H, Ar bombardment will break the chemicalbond and form dangling bonds which react with the O, F, N, H freeradicals and form volatile by-products. This also makes the surface ofthe dielectric film 104 become hydrophilic, pushing some fraction of thefree radicals into the dielectric film 104. Damaged carbon willre-hydroxylate and hydrogen bond with water, which raises an effectivedielectric constant of the dielectric film 104. Various thermalprocesses (e.g., high-temperature anneals) also promote condensation ofadjacent Si—OH groups, increasing their density, and creating voidswithin the dielectric film 104. The treating agent particles 112comprise a re-methylating compound which re-alkylates or re-arylates thedamaged carbon, thus restoring the dielectric constant. An exemplaryembodiment of the re-methylation process comprises an SiOH damagedsurface reacted with RxSi(OCOCH₃)y treating agent particles to yield arepaired surface of SiOSiRx. Replacing Si—OH bonds by Si—O—Si—Rx bondsavoids condensation reactions, and thus void formation. Other exemplaryembodiments comprise treating agent particles which replenish carboncontaining moieties within the dielectric film 104.

FIG. 2B illustrates some embodiments of a self-repairing dielectricmaterial 200B. A chemical reaction initiated between the treating agentparticles 108 and the sidewall damage which creates a repaired sidewall206. The reaction of the treating agent particles 108 with the sidewalldamage consumes the treating agent particles 108 and depletes theirconcentration within the surface region, resulting in a gradientconcentration 208 of the treating agent particles 108 within thedielectric film 104, wherein a density of treating agent particleswithin the surface region of the dielectric film 104 is less than adensity of treating agent particles 108 within a bulk region of thedielectric film 104, the bulk region comprising an interior region ofthe dielectric film 104 other than the surface region. The gradientconcentration 208 of treating agent particles 108 results in continuousdiffusion 210 of the treating agent particles from the bulk region ofthe dielectric film 104 to the surface region of the dielectric film104. Moreover, the larger concentration of treating agent particles 112within the bulk region of the dielectric film 104 will react withcontaminant radicals which diffuse into the dielectric film 104.

To verify the effectiveness of the treating agent particles inincreasing the concentration of carbon containing moieties within adielectric material, a carbon concentration of the dielectric materialmay be measured by techniques such as Energy-dispersive X-rayspectroscopy (EDX) or X-ray Photoelectron Spectroscopy (XPS). FIG. 3Aillustrates a table describing four dielectric material samples for XPSmeasurements of carbon concentration. S1 (602) is an untreateddielectric film. S2 (604) is an etched dielectric film with damage. S3(606) is a self-repairing dielectric film produced by subjectingunpatterned dielectric film to a treating agent particle treatment andcapping with a non-porous cap material prior to etching and ashingprocesses. S4 (608) is an externally-repaired dielectric film producedby subjecting an unpatterned dielectric film to etching and ashingprocesses followed by the treating agent particle treatment.

FIG. 3B illustrates a carbon depletion profile 300B for some embodimentsof self-repairing dielectrics vs. externally-repaired dielectrics asmeasured by XPS, wherein the carbon concentration of Carbon (Atomic %)is shown as a function of sputter depth. In this non-limiting example athickness of a damage region 610 is expressed as a sputter time ofapproximately 120 seconds. It will be appreciated from the concentrationof Carbon given by S1-S4 (602-608) within the thickness of the damageregion 610, that S3 (606) for a self-repairing dielectric film givesessentially the same behavior as S1 (602) for an untreated dielectricfilm (approximately less than a 5% maximum difference in carbonconcentration for sputter times between approximately 0 seconds and 120seconds), whereas for S4 (608) for externally-repaired dielectric filmshows less carbon concentration in the same region (approximatelygreater than a 5% maximum difference in carbon concentration for sputtertimes between approximately 0 seconds and 120 seconds). Thus, for theembodiments of 300B the self-repairing dielectric film demonstratesincreased carbon concentration as compared to the externally-repaireddielectric film. Although FIG. 3B is not meant to be representative ofall sidewall repair processes of a low-k dielectric film in any way, itdoes tend to show that the proposed implementation for a self-repairingporous low-k dielectric film can provide significant improvement incarbon concentration within the region of sidewall damage compared tosome prior art approaches.

FIG. 4 illustrates a flow diagram of some embodiments of a method 400 tocreate a self-repairing dielectric structure. While method 400 isillustrated and described below as a series of acts or events, it willbe appreciated that the illustrated ordering of such acts or events arenot to be interpreted in a limiting sense. For example, some acts mayoccur in different orders and/or concurrently with other acts or eventsapart from those illustrated and/or described herein. In addition, notall illustrated acts may be required to implement one or more aspects orembodiments of the description herein. Further, one or more of the actsdepicted herein may be carried out in one or more separate acts and/orphases.

At 402 a substrate is provided. The substrate comprises a silicon waferor other semiconductor workpiece.

At 404 a dielectric material is formed on the substrate. The dielectricmaterial comprises a porous low-k dielectric (e.g., 2.4≦k≦3.0) or porousultra low-k dielectric (e.g., k<2.4) formed by chemical vapor deposition(CVD) or spin on methods.

At 406 the dielectric material is exposed with treating agent particlessuch that the treating agent particles diffuse into the dielectricmaterial and form a substantially uniform concentration within thedielectric material. The treating agent particles comprisere-methylating compound capable of re-alkylating or re-arylating thedamaged carbon, with a treating agent particle size that is smaller thana first pore size of the dielectric material. The treating agentparticles may further comprises at least one compound having a formula[—SiR₂NR′—]_(n) where n>2 and may be cyclic; R₃SiNR′SiR₃, (R₃Si)₃N;R₃SiNR′₂; R₂Si(NR)₂; RSi(NR′)₃; R_(x)SiCl_(y), R_(x)Si(OH)_(y);R₃SiOSiR′₃; R_(x)Si(OR′)_(y); R_(x)Si(OCOR′)_(y), R_(x)SiH_(y);R_(x)Si[OC(R′)═R″]_(4-x) or combinations thereof, wherein x is aninteger ranging from 1 to 3, y is an integer ranging from 1 to 3 suchthat x+y=4, each R is independently selected from hydrogen and ahydrophobic organic moiety; R′ is hydrogen, or an organic moiety, and R″is an alkyl or carbonyl group.

At 408 dielectric material is capped with a dense low-k dielectric. Thedense low-k dielectric comprises a non-porous dense low-k dielectricwith a second pore size that is smaller than the treating agent particlesize, encapsulating the treating agent particles within the dielectricmaterial.

At 410 the dielectric material is subjected to a patterning stepcomprising coating of the dielectric material with photoresist, aligningthe dielectric material with a patterning mask, and exposing thedielectric material to a radiation source. The radiation creates apattern of developed photoresist corresponding to open regions of thephotomask.

At 412 the dielectric material is subjected to a first process whichintroduces damage within a damage region within the dielectric material,the damage comprising a degradation to an electrical parameter of thedielectric material. The process comprises one or more of ashing,etching, wet or dry chemical cleaning, thermal cycling, or combinationsthereof. The damage comprises a reduction in a concentration of carboncontaining moieties within the damage region.

At 414 the dielectric material is subjected to a second process, whichcomprises an optional activation operation that promotes a reactionbetween the treating agent particles and the damage of the dielectricmaterial. In some embodiments this reaction occurs automatically as thedamage is formed. In other embodiments the reaction may be initiated orenhanced (e.g., faster reaction rate) by an activation operation whichcomprises a high-temperature process, ultra-violet cure, or otherenergy-transferring process.

At 416 a reaction is initiated between the treating agent particles andthe damage of the dielectric material, wherein the reaction repairs thedamage, restoring the electrical parameter to approximately its originalvalue. The reaction comprises a chemical reaction between treating agentparticles comprising a re-methylating compound which re-alkylates orre-arylates damaged carbon within a surface region of the dielectricmaterial. The chemical reaction comprises consuming the treating agentparticles within the damage region within the surface region of thedielectric material, resulting in a gradient concentration of thetreating agent particles within the dielectric material. In someembodiments the reaction occurs simultaneously, while in otherembodiments an activation energy is either required to initiate thereaction, or may enhance the reaction.

At 418 the gradient concentration of treating agent particles results incontinuous diffusion the treating agent particles from the center of thedielectric material to the surface of the dielectric material,continuously repairing damage to the dielectric material.

It will also be appreciated that equivalent alterations and/ormodifications may occur to one of ordinary skill in the art based upon areading and/or understanding of the specification and annexed drawings.The disclosure herein includes all such modifications and alterationsand is generally not intended to be limited thereby. In addition, whilea particular feature or aspect may have been disclosed with respect toonly one of several implementations, such feature or aspect may becombined with one or more other features and/or aspects of otherimplementations as may be desired. Furthermore, to the extent that theterms “includes”, “having”, “has”, “with”, and/or variants thereof areused herein; such terms are intended to be inclusive in meaning—like“comprising.” Also, “exemplary” is merely meant to mean an example,rather than the best. It is also to be appreciated that features, layersand/or elements depicted herein are illustrated with particulardimensions and/or orientations relative to one another for purposes ofsimplicity and ease of understanding, and that the actual dimensionsand/or orientations may differ substantially from that illustratedherein.

Therefore, the present disclosure relates to a structure and method tocreate a self-repairing dielectric material for semiconductor deviceapplications. The method of encapsulating treating agent particleswithin a porous dielectric material allows for continuous self-repair ofdamage induced on the surface during etching, as well as reacting withany contaminate radicals which may diffuse into dielectric material as abi-product of etching. The method of encapsulating treating agentparticles within a porous dielectric material prior to etching alsoreduces the number of processing steps required to repair the film,since the formation of the porous dielectric material and an exposure totreating agent particles may be performed in-situ in a single processingstep, as opposed to multiple steps if the dielectric material is formedand repaired after etching.

In some embodiments the present disclosure relates to a method to createa self-repairing low-k dielectric material. A dielectric material isformed on a substrate and exposed to treating agent particles such thatthe treating agent particles diffuse into the dielectric material. A capmaterial ids formed above the dielectric material to encapsulate thetreating agent particles within the dielectric material. A first processforms damage within a damage region of the dielectric material,comprising a degradation to an electrical parameter of the dielectricmaterial. A reaction is initiated between the treating agent particlesand the damage region to restore the electrical parameter toapproximately its original value. The reaction may occur automaticallyas the damage is formed, or may be initiated or enhanced by a secondprocess comprising an activation operation which comprises ahigh-temperature process, ultra-violet cure, or otherenergy-transferring process.

In some embodiments the present disclosure relates to a method offorming a microelectronic device. A porous dielectric material is formedon a substrate, and exposed to treating agent particles, wherein thetreating agent particles comprise a treating agent particle size that issmaller than a first pore size of the porous dielectric, such that thetreating agent particles diffuse into the dielectric. A non-porous capmaterial is formed above the dielectric material, wherein the non-porouscap material comprises a second pore size that is smaller than thetreating agent particle size, which encapsulates the treating agentparticles within the dielectric material.

The dielectric material is then subjected to a process which reduces aconcentration of carbon containing moieties within a damage region ofthe porous dielectric material, and results in a degradation to anelectrical parameter of the dielectric material. A reaction is theninitiated between the treating agent particles and the damage region ofthe dielectric material, wherein the reaction increases theconcentration of carbon containing moieties within the damage region,restoring the electrical parameter to approximately its original value.

In some embodiments the present disclosure relates to a self-repairingdielectric structure, comprising a porous dielectric material formed onthe a semiconductor workpiece which has been exposed to a plurality oftreating agent particles. The treating agent particles diffuse into theporous dielectric material. The treating agent particles comprise atreating agent particle size which is smaller than a first pore size ofthe porous dielectric material such that the treating agent particlesdiffuse freely thru the dielectric material to repair damage within theporous dielectric material.

What is claimed is:
 1. A method to create a self-repairing dielectricmaterial, comprising: forming a dielectric material on a substrate;exposing the dielectric material to treating agent particles configuredto diffuse into the dielectric material; forming a cap material on anouter surface of the dielectric material to encapsulate the diffusedtreating agent particles within the dielectric material; and afterexposing the dielectric material to the treating agent particles,damaging the dielectric material to form a damaged region within thedielectric material, wherein the diffused treating agent particles areconfigured to react with the damaged region to repair damage to thedielectric material.
 2. The method of claim 1, wherein damaging thedielectric material reduces a concentration of carbon containingmoieties within the damaged region; and wherein a reaction between thediffused treating agent particles and the damaged region increases theconcentration of carbon containing moieties within the damaged region.3. The method of claim 1, wherein the dielectric material is a porousdielectric material with a first pore size that is larger than atreating agent particle size of the diffused treating agent particles;and wherein the cap material has a second pore size that is smaller thanthe treating agent particle size.
 4. The method of claim 1, wherein thedamaged region is located within a surface region on the outer surfaceof the dielectric material.
 5. The method of claim 4, wherein a reactionbetween the diffused treating agent particles and the damaged regionlowers a concentration of the diffused treating agents near the surfaceregion, resulting in a gradient concentration of the diffused treatingagent particles within the dielectric material; and wherein the gradientconcentration of the diffused treating agent particles results infurther diffusion of the diffused treating agent particles from a bulkregion of the dielectric material to the surface region of thedielectric material.
 6. The method of claim 1, further comprisingperforming a high-temperature process or ultra-violet cure to initiate areaction between the diffused treating agent particles and the damagedregion.
 7. The method of claim 1, wherein a reaction between thediffused treating agent particles and the damaged region decreases adielectric constant of the dielectric material.
 8. A method, comprising:forming a porous dielectric material on a substrate, wherein the porousdielectric material has an initial dielectric constant when initiallyformed on the substrate; exposing the porous dielectric material totreating agent particles, which comprise a treating agent particle sizethat is smaller than a pore size of the porous dielectric material, suchthat the treating agent particles diffuse into the porous dielectricmaterial; forming a cap material above the porous dielectric material,the cap material comprising a second pore size that is smaller than thetreating agent particle size, so as to encapsulate the diffused treatingagent particles within the porous dielectric material; after exposingthe dielectric material to the treating agent particles, damaging theporous dielectric material, wherein damaging the porous dielectricmaterial degrades the initial dielectric constant of the porousdielectric material to a degraded dielectric constant; and initiating areaction between the diffused treating agent particles and a damagedregion of the porous dielectric material to restore the degradeddielectric constant to a value approximately equal to the initialdielectric constant.
 9. The method of claim 8, wherein damaging theporous dielectric material is performed by a process comprising one ormore of ashing, etching, chemical cleaning, or thermal cycling.
 10. Themethod of claim 9, wherein the reaction between the diffused treatingagent particles and the damaged region lowers a concentration of thediffused treating agent particles near a surface region, resulting in agradient concentration of the diffused treating agent particles withinthe dielectric material; and wherein the gradient concentration of thediffused treating agent particles results in further diffusion of thediffused treating agent particles from a bulk region of the porousdielectric material to the surface region of the porous dielectricmaterial.
 11. The method of claim 10, wherein the gradient concentrationcomprises a difference in carbon concentration between the bulk regionand the damage region of the dielectric material that is greater than orequal to approximately 5%.
 12. The method of claim 8, wherein thediffused treating agent particles comprise a re-methylating compoundconfigured to re-alkylate or re-arylate the damage region.
 13. Themethod of claim 8, wherein damage to the damaged region of the porousdielectric material replaces Si—CH₃ bonds with Si—OH bonds, and whereinthe diffused treating agent particles are configured to re-alkylate orre-arylate the Si—OH bonds.
 14. The method of claim 8, wherein damagingthe porous dielectric material reduces a concentration of carboncontaining moieties within the damaged region of the porous dielectricmaterial; and wherein the reaction between the diffused treating agentparticles and the damage region increases the concentration of carboncontaining moieties within the damage region.
 15. A method, comprising:forming a dielectric material over a substrate; diffusing treating agentparticles into the dielectric material; and after diffusing the treatingagent particles into the dielectric material, damaging the dielectricmaterial to form a damaged region within the dielectric material,wherein the treating agent particles within the dielectric material areconfigured to repair the damaged region.
 16. The method of claim 15,wherein damaging the dielectric material degrades a dielectric constantof the dielectric material from an initial dielectric constant to adegraded dielectric constant; and wherein the diffused treating agentparticles react with the damaged region to restore the degradeddielectric constant to a value approximately equal to the initialdielectric constant.
 17. The method of claim 15, wherein the dielectricmaterial comprises a porous material having a plurality of pores withpore sizes that are larger than a treating agent particle size of thediffused treating agent particles.
 18. The method of claim 15, furthercomprising forming a cap material on a surface of the dielectricmaterial, after diffusing the treating agent particles into thedielectric material, to encapsulate the diffused treating agentparticles within the dielectric material.
 19. The method of claim 15,wherein damaging the dielectric material comprises one or more ofashing, etching, chemical cleaning, or thermal cycling.
 20. The methodof claim 15, wherein damage to the dielectric material replaces Si—CH₃bonds with Si—OH bonds, and wherein the diffused treating agentparticles are configured to re-alkylate or re-arylate the Si—OH bonds.